CN118440585B - Antifouling paint for marine application facilities and preparation method thereof - Google Patents
Antifouling paint for marine application facilities and preparation method thereof Download PDFInfo
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- CN118440585B CN118440585B CN202410902674.4A CN202410902674A CN118440585B CN 118440585 B CN118440585 B CN 118440585B CN 202410902674 A CN202410902674 A CN 202410902674A CN 118440585 B CN118440585 B CN 118440585B
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- aluminum nitride
- tetraethoxysilane
- antifouling paint
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- WREWAMXVXPPKQU-UHFFFAOYSA-N 1-dodecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+]1CN(C)C=C1 WREWAMXVXPPKQU-UHFFFAOYSA-N 0.000 claims description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of antifouling paint, and provides an antifouling paint for marine application equipment and a preparation method thereof, the components of the antifouling paint comprise polyether polyurethane, tetraethoxysilane modified aluminum nitride, imidazole ionic liquid, a dispersing agent and a defoaming agent. The tetraethoxysilane modified aluminum nitride and the ionic liquid in the antifouling paint have the effects of physical antifouling and chemical antifouling; in addition, the silicon hydroxyl and siloxane bond in tetraethoxysilane modified aluminum nitride can react with hydroxyl or silicate group in concrete to form strong chemical bond, so as to increase the adhesive force of the paint and the concrete.
Description
Technical Field
The invention relates to the technical field of anti-fouling paint, in particular to an anti-fouling paint for marine application facilities and a preparation method thereof.
Background
The marine concrete is widely applied to ocean engineering structures such as bridges, wharfs, breakwater and the like. These structures are exposed to harsh marine environments for long periods of time and are vulnerable to seawater, wave impingement, and marine organism attachment. Among them, the attachment of marine organisms (such as algae, barnacles and shellfish) leads to an increase in the roughness of the surface of the structure, thereby affecting the hydrodynamic properties and durability of the material. These organisms can accelerate the corrosion of the concrete, reducing the service life of the engineering structure.
The antifouling paint contains active ingredients capable of inhibiting or killing attached marine organisms, and can prevent the attachment of the marine organisms by forming a layer of protective film on the surface of the concrete, so that the surface of the concrete is kept clean, and the damage of the attachment of the marine organisms to the concrete is effectively solved. Although the application of the antifouling paint in marine concrete has remarkable advantages, the following problems still exist in practical application: the adhesive force of the antifouling paint on the concrete surface is often insufficient due to the porous and rough surface of the concrete and the long-time bearing of wave impact, salt spray corrosion, mechanical abrasion and the like, the antifouling paint is easy to peel off after long-term use, the durability is insufficient, the effective period of the antifouling paint is shortened, and the maintenance cost is increased, so that the antifouling paint is one of the main problems affecting the effect of the antifouling paint.
Disclosure of Invention
In view of the above, the invention provides an antifouling paint for marine application equipment with strong adhesive force and long antifouling validity period and a preparation method thereof.
The technical scheme of the invention is realized as follows: in one aspect, the invention provides an antifouling paint for marine application, wherein the antifouling paint comprises polyether polyurethane, tetraethoxysilane modified aluminum nitride, imidazole ionic liquid, a dispersing agent and a defoaming agent.
The polyether polyurethane is used as a paint base material of the antifouling paint, has good characteristics of salt mist resistance, acid and alkali resistance, oil resistance and other chemical corrosion resistance, and also has good low temperature resistance and crack resistance, so that the service life of the antifouling paint in marine paint is prolonged.
Aluminum nitride has similar thermal expansion performance with concrete at different temperatures, which reduces internal stress accumulation of the coating during temperature change and reduces the risks of stripping and cracking of the coating. Tetraethoxysilane (TEOS) modified aluminum nitride introduces silicon hydroxyl and siloxane bonds on the surface of aluminum nitride particles, and the silicon hydroxyl and siloxane bonds can react with hydroxyl or silicate groups in concrete to form strong chemical bonding, so that the adhesive force of the paint and the concrete is increased. In addition, tetraethoxysilane modifies aluminum nitride to form a layer of compact inorganic oxide coating on the surface of aluminum nitride, so that hydrolysis of the aluminum nitride can be effectively prevented, and stability of the aluminum nitride is enhanced. Tetraethoxysilane modified aluminum nitride can improve the defects of poor ultraviolet resistance and yellowing of polyether polyurethane.
Biofilm formation is an important step in marine organism attachment. The imidazole ionic liquid can effectively kill bacteria attached at the initial stage, prevent bacterial colony formation and prevent the initial formation of a biological film; the hydrophobic hydrocarbon chain part of the imidazole cation can be inserted into the cell membrane of microorganisms to damage the integrity of the cell membrane, so that the cell content leaks, thereby killing bacteria and other microorganisms, preventing marine organisms from adhering and propagating on the surface of the coating, and further playing an antifouling role. The ionic liquid lowers the surface energy of the coating, making it difficult for marine organisms to find attachment points on the surface of the coating, thereby reducing the stability and growth rate of the biofilm.
The tetraethoxysilane modified aluminum nitride can improve the surface morphology of the coating, so that the coating is smoother and denser, the possibility of microorganism adhesion is reduced, a synergistic effect is formed with the antifouling performance of the imidazole ionic liquid, and the comprehensive antifouling effect of the coating is further improved. The simultaneous existence of the inorganic aluminum nitride particles and the imidazole ionic liquid can realize a multiple antifouling mechanism: the combination of physical barriers (preventing the attachment of organisms) and chemical actions (killing or inhibiting microorganisms) enhances the durability of the anti-fouling effect.
In addition, on the basis of the technical scheme, preferably, the anti-fouling paint comprises, by weight, 80-100 parts of polyether polyurethane, 10-20 parts of tetraethoxysilane modified aluminum nitride, 8-15 parts of imidazole ionic liquid, 3-5 parts of a dispersing agent and 2-5 parts of a defoaming agent.
On the basis of the technical scheme, preferably, the preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: dissolving tetraethoxysilane in ethanol, adding hydrochloric acid solution, and stirring for reacting for 2-3 h; adding aluminum nitride powder, continuously stirring to uniformly mix the aluminum nitride powder, and aging to form a homogeneous gel; drying the gel and calcining at 400-650 ℃ to obtain tetraethoxysilane modified aluminum nitride.
On the basis of the above technical solution, preferably, the tetraethoxysilane: the mass ratio of the aluminum nitride is 6-8:1.
On the basis of the technical scheme, preferably, the ionic liquid is one of 1-ethyl-3-methylimidazole lactate, 1-dodecyl-3-methylimidazole chloride and 1-butyl-3-methylimidazole acetate.
The lactic acid, chloride ions and acetate in the ionic liquid have certain antibacterial property, and the ionic structures of the lactate and the acetate can also enable the lactate and the acetate to permeate into marine pollutants to damage adhesion matrixes and prevent the formation of biological films. The hydrophobicity of the dodecyl chains makes the surface of the coating more hydrophobic, reducing the adsorption of moisture and thus reducing the attachment rate of marine organisms.
In addition, hydroxyl and carboxyl in the 1-ethyl-3-methylimidazole lactate, chloride ions in the 1-dodecyl-3-methylimidazole chloride and acetate in the 1-butyl-3-methylimidazole acetate can also generate hydrogen bond or ion-dipole interaction with the surface of the concrete, so that the adhesive force of the coating and the concrete is improved, and the polarity of the acetate makes the coating and the concrete show more excellent combination with porous and polar materials such as the concrete.
Based on the technical scheme, the novel polylactic acid coating also preferably comprises 6-10 parts by weight of polylactic acid.
Polylactic acid is slowly degraded in the marine environment, and the antifouling active ingredient ionic liquid is gradually released, so that marine organisms are prevented from adhering and propagating on the surface of the coating. The slow release characteristic ensures long-term persistence of the antifouling effect and reduces the requirement of frequent maintenance.
On the basis of the technical scheme, the chlorinated paraffin is preferable to further comprise 5-8 parts by weight of chlorinated paraffin.
The chlorinated paraffin forms a compact matrix structure in the coating, so that the polylactic acid can be physically protected, the degradation speed of the polylactic acid is reduced when the polylactic acid is eroded by the marine environment, and the slow release effect of the polylactic acid is longer due to the protection effect. The chlorinated paraffin and the polylactic acid have good compatibility in the coating, and can be mutually embedded or mutually wrapped. The structure not only improves the overall stability of the coating, but also ensures that the anti-fouling agent can be uniformly distributed in the whole coating, and further prolongs the effective release time of the anti-fouling agent. In addition, the chlorinated paraffin can also fill micro-pores between the coating and the concrete, provide additional mechanical locking force, enhance the overall adhesive force and prolong the antifouling effect.
On the basis of the technical scheme, preferably, the dispersing agent is one of fatty alcohol polyoxyethylene ether, alkyl polyglucoside and fatty acid methyl ester ethoxylate; the defoamer is polyether defoamer or organic silicon defoamer.
On the other hand, the invention also provides a preparation method of the antifouling paint for the marine application equipment, which comprises the following steps:
s1, adding polyether polyurethane into an organic solvent, and stirring to dissolve the polyether polyurethane to obtain a polyether polyurethane mixture;
S2, adding tetraethoxysilane modified aluminum nitride and a dispersing agent into the polyether polyurethane mixture, and stirring for 0.5-1 h to enable the nano particles to be uniformly dispersed;
and S3, sequentially adding polylactic acid, chlorinated paraffin, imidazole ionic liquid and ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring for reaction, finally adding a defoaming agent, and standing for defoaming after stirring uniformly.
On the basis of the technical scheme, preferably, the ethylene glycol diglycidyl ether: the weight ratio of the polyether polyurethane is 1-5: 80-100.
The ethylene glycol diglycidyl ether crosslinking agent can form a three-dimensional network structure, so that the mechanical strength, chemical corrosion resistance and wear resistance of the coating are further improved.
Compared with the prior art, the antifouling paint for the marine application equipment and the preparation method thereof have the following beneficial effects:
(1) The tetraethoxysilane modified aluminum nitride and the ionic liquid in the antifouling paint have the combined effect of physical antifouling and chemical antifouling, wherein the tetraethoxysilane modified aluminum nitride provides a smooth and compact physical barrier, and the ionic liquid kills or inhibits microorganism adhesion and propagation, so that the chemical protection property is improved. In addition, tetraethoxysilane modified aluminum nitride also increases the adhesive force of the paint and concrete, and achieves the technical effect of prolonging the antifouling validity period of the paint.
(2) The slow degradability of polylactic acid in the anti-fouling paint plays a role in slowly releasing the anti-fouling active ingredient ionic liquid, ensures the long-term persistence of the anti-fouling effect and reduces the requirement of frequent maintenance.
(3) The chlorinated paraffin in the antifouling paint plays a role in physically protecting the polylactic acid, so that the degradation speed of the polylactic acid is reduced when the polylactic acid is eroded by the marine environment, and the antifouling effective period is prolonged; meanwhile, the chlorinated paraffin can also improve the mechanical locking force of the coating and the concrete, and enhance the adhesive force of the coating.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The reaction reagents of the invention are all purchased in the market, wherein polyether polyurethane is purchased from Jiangsu hong guang plastic raw materials limited company, model 9868DU; polyether defoamers (model P-20, P-12, P-06) and silicone defoamers (model MY-220, MY-230, MY-208) are all purchased from Shandong Meiyu chemical Co., ltd, imidazole ion liquid is all purchased from Wuhan Bei Leshe biological medicine technology Co., ltd, chlorinated paraffin and polylactic acid are all purchased from Shanghai Michelin biochemical technology Co., ltd, aluminum nitride is purchased from Tinpida specialty ceramic Co., ltd, tetraethoxysilane is purchased from Durun (Shandong) New Material Co.
Example 1
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-ethyl-3-methylimidazole lactate, fatty alcohol polyoxyethylene ether and polyether defoamer P-20.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 60g of tetraethoxysilane is dissolved in 250mL of absolute ethyl alcohol, 100mL of 4.6mmol/L hydrochloric acid aqueous solution is added, and the mixture is stirred and reacted for 2h to form a colloidal solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging at 40 ℃ for 12 hours after mixing to form homogeneous gel; drying the gel at 100 ℃ and calcining at 400 ℃ for 4 hours to obtain tetraethoxysilane modified aluminum nitride.
The preparation method of the antifouling paint comprises the following steps:
s1, adding 800g of polyether polyurethane into 150g of methyl ethyl ketone and 200g of N, N-dimethylformamide serving as organic solvents, and stirring to dissolve the mixture to obtain a polyether polyurethane mixture.
S2, adding 100g of tetraethoxysilane modified aluminum nitride and 30g of fatty alcohol polyoxyethylene ether into the polyether polyurethane mixture, and stirring for 0.5h to uniformly disperse the nano particles.
S3, sequentially adding 80g of 1-ethyl-3-methylimidazole lactate and 10g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 60 ℃ for reaction for 3 hours, finally adding 20g of polyether defoamer P-20, and standing for defoaming after stirring uniformly.
Example 2
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-ethyl-3-methylimidazole lactate, polylactic acid, fatty alcohol polyoxyethylene ether and polyether defoamer P-20.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 60g of tetraethoxysilane is dissolved in 250mL of absolute ethyl alcohol, 100mL of 4.6mmol/L hydrochloric acid aqueous solution is added, and the mixture is stirred and reacted for 2h to form a colloidal solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging at 40 ℃ for 12 hours after mixing to form homogeneous gel; drying the gel at 100 ℃ and calcining at 400 ℃ for 4 hours to obtain tetraethoxysilane modified aluminum nitride.
The preparation method of the antifouling paint comprises the following steps:
s1, adding 800g of polyether polyurethane into 150g of methyl ethyl ketone and 200g of N, N-dimethylformamide serving as organic solvents, and stirring to dissolve the mixture to obtain a polyether polyurethane mixture.
S2, adding 100g of tetraethoxysilane modified aluminum nitride and 30g of fatty alcohol polyoxyethylene ether into the polyether polyurethane mixture, and stirring for 0.5h to uniformly disperse the nano particles.
S3, sequentially adding 80g of 1-ethyl-3-methylimidazole lactate, 60g of polylactic acid and 10g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 60 ℃ for reaction for 3 hours, finally adding 20g of polyether defoamer P-20, stirring uniformly, and standing for defoaming.
Example 3
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-ethyl-3-methylimidazole lactate, polylactic acid, chlorinated paraffin, fatty alcohol polyoxyethylene ether and polyether defoamer P-20.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 60g of tetraethoxysilane is dissolved in 250mL of absolute ethyl alcohol, 100mL of 4.6mmol/L hydrochloric acid aqueous solution is added, and the mixture is stirred and reacted for 2h to form a colloidal solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging at 40 ℃ for 12 hours after mixing to form homogeneous gel; drying the gel at 100 ℃ and calcining at 400 ℃ for 4 hours to obtain tetraethoxysilane modified aluminum nitride.
The preparation method of the antifouling paint comprises the following steps:
s1, adding 800g of polyether polyurethane into 150g of methyl ethyl ketone and 200g of N, N-dimethylformamide serving as organic solvents, and stirring to dissolve the mixture to obtain a polyether polyurethane mixture.
S2, adding 100g of tetraethoxysilane modified aluminum nitride and 30g of fatty alcohol polyoxyethylene ether into the polyether polyurethane mixture, and stirring for 0.5h to uniformly disperse the nano particles.
S3, sequentially adding 80g of 1-ethyl-3-methylimidazole lactate, 60g of polylactic acid, 50g of chlorinated paraffin and 10g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 60 ℃ for reaction for 3 hours, finally adding 20g of polyether defoamer P-20, stirring uniformly, and standing for defoaming.
Example 4
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-dodecyl-3-methylimidazole chloride, polylactic acid, chlorinated paraffin, alkyl polyglucoside and an organosilicon defoamer MY-220.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 80g of tetraethoxysilane is dissolved in 350mL of ethanol, 100mL of 4.6mmol/L hydrochloric acid solution is added, and the mixture is stirred and reacted for 3 hours to form a colloid solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging at 70 ℃ for 10 hours after mixing to form homogeneous gel; drying the gel at 120 ℃ and calcining at 650 ℃ for 2 hours to obtain tetraethoxysilane modified aluminum nitride.
The preparation method of the antifouling paint comprises the following steps:
s1, adding 900g of polyether polyurethane into 200g of methyl ethyl ketone and 250g of N, N-dimethylformamide serving as organic solvents, and stirring to dissolve the mixture to obtain a polyether polyurethane mixture.
S2, 150g of tetraethoxysilane modified aluminum nitride and 35g of alkyl polyglucoside are added into the polyether polyurethane mixture, and stirring is carried out for 1h to enable the nano particles to be uniformly dispersed.
S3, sequentially adding 70g of polylactic acid, 60g of chlorinated paraffin, 100g of 1-dodecyl-3-methylimidazole chloride and 20g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 60 ℃ for reaction for 3 hours, and finally adding 30g of organosilicon defoamer MY-220, stirring uniformly, and standing for defoaming.
Example 5
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-butyl-3-methylimidazole acetate, polylactic acid, chlorinated paraffin, fatty acid methyl ester ethoxylate and polyether defoamer P-12.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 70g of tetraethoxysilane is dissolved in 300mL of ethanol, 100mL of 4.6mmol/L hydrochloric acid solution is added, and the mixture is stirred and reacted for 2.5h to form a colloid solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging at 60 ℃ for 11 hours after mixing to form homogeneous gel; drying the gel at 110 ℃ and calcining at 550 ℃ for 3 hours to obtain tetraethoxysilane modified aluminum nitride. The preparation method of the antifouling paint comprises the following steps:
s1, 1000g of polyether polyurethane is added into 200g of methyl ethyl ketone and 300g of N, N-dimethylformamide as organic solvents, and stirred to be dissolved, so as to obtain a polyether polyurethane mixture.
S2, adding 200g of tetraethoxysilane modified aluminum nitride and 50g of fatty acid methyl ester ethoxylate into the polyether polyurethane mixture, and stirring for 1h to uniformly disperse the nano particles.
S3, sequentially adding 90g of polylactic acid, 70g of chlorinated paraffin, 120g of 1-butyl-3-methylimidazole acetate and 50g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 70 ℃ for reaction for 3 hours, finally adding 40g of polyether defoamer P-12, stirring uniformly, and standing for defoaming.
Example 6
The antifouling paint for marine application of the present embodiment comprises the following components: polyether polyurethane, tetraethoxysilane modified aluminum nitride, 1-ethyl-3-methylimidazole lactate, polylactic acid, chlorinated paraffin, fatty alcohol polyoxyethylene ether and an organosilicon defoamer MY-230.
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: 75g of tetraethoxysilane is dissolved in 330mL of ethanol, 100mL of 4.6mmol/L hydrochloric acid solution is added, and the mixture is stirred and reacted for 3 hours to form a colloid solution; adding 10g of aluminum nitride powder, continuously stirring to uniformly mix, and aging for 10 hours at 65 ℃ after mixing to form homogeneous gel; drying the gel at 120 ℃ and calcining at 500 ℃ for 3 hours to obtain tetraethoxysilane modified aluminum nitride.
The preparation method of the antifouling paint comprises the following steps:
s1, adding 950g of polyether polyurethane into 250g of methyl ethyl ketone and 200g of N, N-dimethylformamide serving as organic solvents, and stirring to dissolve the mixture to obtain a polyether polyurethane mixture.
S2, adding 180g of tetraethoxysilane modified aluminum nitride and 50g of fatty alcohol polyoxyethylene ether into the polyether polyurethane mixture, and stirring for 1h to uniformly disperse the nano particles.
S3, sequentially adding 100g of polylactic acid, 80g of chlorinated paraffin, 150g of 1-ethyl-3-methylimidazole lactate and 40g of ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring at 80 ℃ for reaction for 2 hours, finally adding 45g of organosilicon defoamer MY-230, stirring uniformly, and standing for defoaming.
Comparative example 1
Comparative example 1 was different from example 1 in that aluminum nitride was not modified, the amount of aluminum nitride was 14g, and the rest was the same.
Comparative example 2
Comparative example 2 differs from example 1 in the absence of tetraethoxysilane modified aluminum nitride, the remainder being the same.
Comparative example 3
Comparative example 3 differs from example 1 in that the amount of tetraethoxysilane modified aluminum nitride used is outside the scope of the present application, specifically 220g, and the remainder are the same.
Comparative example 4
Comparative example 4 differs from example 1 in the absence of the imidazole-based ionic liquid, the remainder being the same.
Comparative example 5
Comparative example 5 differs from example 1 in that the amount of the imidazole-based ionic liquid used was outside the limit of the present application, specifically 170g, and the rest was the same.
Comparative example 6
Comparative example 6 differs from example 1 in that the preparation method of the antifouling paint lacks the ethylene glycol diglycidyl ether crosslinking agent, and the rest is the same.
In order to verify the antifouling effect of the antifouling paint, the prepared antifouling paint is uniformly coated on the surface of concrete, the thickness of the coating is 500 mu m, and the adhesive force, corrosion resistance, antifouling property and the like of the coating are detected.
And (3) adhesive force detection: coating adhesion was tested with reference to standard GB/T1720-2020. Impact resistance detection: the impact resistance of the coatings was tested with reference to standard GB/T1732-2020. And (3) corrosion resistance detection: with reference to the standard GB1763-79, the samples are respectively placed in 10wt% of H 2SO4 solution, 10wt% of NaOH solution and 10wt% of NaCl solution for 10d, and the phenomena of bubbling, falling off, cracking and the like of the coating are checked, wherein the bubbling rate is the proportion of the bubble point of the surface of the coating to the whole surface of the coating.
TABLE 1 coating Performance test
As shown in Table 1, the antifouling paint of the present invention has high adhesion, is resistant to seawater impact, and is resistant to acid, alkali and salt corrosion examples 1 to 3, and the comprehensive properties of the paint are improved after polylactic acid and chlorinated paraffin are added. Comparative examples 1-6 show that the comprehensive performance of the paint is reduced due to the lack of tetraethoxysilane modified aluminum nitride and imidazole ionic liquid components, so that the synergistic effect of tetraethoxysilane modified aluminum nitride and imidazole ionic liquid has positive effects on the adhesive force of the antifouling paint on the concrete surface and the seawater scouring resistance and corrosion resistance of the antifouling paint.
Inhibition of algae attachment assay: the antifouling coating samples of the examples and comparative examples were immersed in seawater, and a quantitative amount of diatom liquid was added, respectively, and after 6 months and 1 year, the attached percentage of diatom was observed.
TABLE 2 algae attachment inhibition test
Table 2 shows that the anti-fouling paint prepared by the invention has no adhesion of diatom when tested for 6 months, the adhesion rate of diatom is less than 0.5% when tested for 12 months, and still can achieve higher anti-fouling performance, and from examples 1-3, the adhesion rate of diatom is reduced after polylactic acid and chlorinated paraffin are added, thereby proving the slow release performance of polylactic acid and chlorinated paraffin in the paint, continuously and slowly releasing the ionic liquid of the anti-fouling agent, and prolonging the anti-fouling performance of the paint. From comparative examples 1 to 6, the antifouling effect of comparative example 4 is the worst, thus proving the importance of imidazole ionic liquid in terms of chemical antifouling; comparative example 2 lacking tetraethoxysilane modified aluminum nitride also had poor anti-fouling effect, demonstrating the importance of tetraethoxysilane modified aluminum nitride physical anti-fouling; the lack of the ethylene glycol diglycidyl ether crosslinking agent deteriorates the overall properties of the antifouling paint, thereby affecting the antifouling property. Comparative examples 3 and 5 show that increasing the amounts of tetraethoxysilane modified aluminum nitride and imidazole ionic liquids did not increase the antifouling properties, but rather affected the overall performance and stability of the coating, and thus the antifouling properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. An antifouling paint for marine application facilities, which is characterized in that: the components of the antifouling paint comprise polyether polyurethane, tetraethoxysilane modified aluminum nitride, imidazole ionic liquid, ethylene glycol diglycidyl ether, a dispersing agent and a defoaming agent;
The preparation method of the tetraethoxysilane modified aluminum nitride comprises the following steps: dissolving tetraethoxysilane in ethanol, adding hydrochloric acid solution, and stirring for reacting for 2-3 h; adding aluminum nitride powder, continuously stirring to uniformly mix the aluminum nitride powder, and aging to form a homogeneous gel; drying the gel and calcining at 400-650 ℃ to obtain tetraethoxysilane modified aluminum nitride.
2. An in-sea application antifouling paint according to claim 1, wherein: the anti-fouling paint comprises, by weight, 80-100 parts of polyether polyurethane, 10-20 parts of tetraethoxysilane modified aluminum nitride, 8-15 parts of imidazole ionic liquid, 3-5 parts of a dispersing agent and 2-5 parts of a defoaming agent.
3. An in-sea application antifouling paint according to claim 1, wherein: the tetraethoxysilane: the mass ratio of the aluminum nitride is 6-8:1.
4. An in-sea application antifouling paint according to claim 1, wherein: the imidazole ionic liquid is one of 1-ethyl-3-methylimidazole lactate, 1-dodecyl-3-methylimidazole chloride and 1-butyl-3-methylimidazole acetate.
5. An in-sea application antifouling paint according to claim 2, wherein: and 6-10 parts by weight of polylactic acid.
6. An in-sea application antifouling paint according to claim 5, wherein: also comprises 5-8 parts by weight of chlorinated paraffin.
7. An in-sea application antifouling paint according to claim 4, wherein: the dispersing agent is one of fatty alcohol polyoxyethylene ether, alkyl polyglucoside and fatty acid methyl ester ethoxylate; the defoamer is polyether defoamer or organic silicon defoamer.
8. The method for preparing the antifouling paint for the marine application equipment as claimed in claim 6, wherein: the method comprises the following steps:
s1, adding polyether polyurethane into an organic solvent, and stirring to dissolve the polyether polyurethane to obtain a polyether polyurethane mixture;
S2, adding tetraethoxysilane modified aluminum nitride and a dispersing agent into the polyether polyurethane mixture, and stirring for 0.5-1 h to enable the nano particles to be uniformly dispersed;
and S3, sequentially adding polylactic acid, chlorinated paraffin, imidazole ionic liquid and ethylene glycol diglycidyl ether into the dispersion liquid in the step S2, stirring for reaction, finally adding a defoaming agent, and standing for defoaming after stirring uniformly.
9. The method for preparing the antifouling paint for the marine application equipment as claimed in claim 8, wherein: the ethylene glycol diglycidyl ether: the weight ratio of the polyether polyurethane is 1-5: 80-100.
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| CN103160205A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Ionic liquid marine antifouling coating |
| CN106280969A (en) * | 2016-09-08 | 2017-01-04 | 山东船舶技术研究院 | Preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas |
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| AU3682095A (en) * | 1994-09-23 | 1996-04-09 | Duke University | Aquatic surface antifouling compositions |
| JP2005132924A (en) * | 2003-10-29 | 2005-05-26 | Kamoi Kakoshi Kk | Antifouling composition for readily removing attached aquatic life, article coated with the composition and preventing aquatic life adhesion and method for preventing aquatic life adhesion |
| CN1278995C (en) * | 2005-04-07 | 2006-10-11 | 上海交通大学 | Method for preventing hydrolysis of aluminium nitride |
| KR101872254B1 (en) * | 2017-12-19 | 2018-06-29 | 유재형 | Finishing coating composition for surface of concrete structure and method for finishing coating surface of concrete structure therewith |
| CN108517139A (en) * | 2018-04-15 | 2018-09-11 | 陈超 | A kind of environment-friendly water-based polyurethane coating of automatically cleaning and preparation method thereof |
| CN109294431A (en) * | 2018-09-27 | 2019-02-01 | 佛山九陌科技信息咨询有限公司 | A kind of marine antifouling coating |
| CN113527627A (en) * | 2021-08-18 | 2021-10-22 | 中国科学院海洋研究所 | Polylactic acid polycarbonate-based polyurethane with self-repairing function and preparation method and application thereof |
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| CN103160205A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Ionic liquid marine antifouling coating |
| CN106280969A (en) * | 2016-09-08 | 2017-01-04 | 山东船舶技术研究院 | Preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas |
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